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Fig. 1. Organocatalytic photochemical strategies for the stereoselective radical α-perfluoroalkylation of (a) aldehydes and (b) β-ketoesters. (c) Design plan for the stereocontrolled radical perfluoroalkylation of enals at the remote γ-carbon via excitation of an EDA complex III between a catalytic dienamine II and perfluoroalkyl iodides. PTC: phase transfer catalyst; EDA: electron donor–acceptor; RF: perfluoroalkyl chain.